Catalytic cracking



Patented Apr. 21, 1942 CATALYTIC CBACKIN G Charles L. Thomas, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 111;, a

corporation of Delaware No Drawing. Application July 8, 1940,

Serial No. 344,373

9 Claims.

This invention relates to improved media for the transfer of heat particularly in catalytic reactions and is a continuation-in-part of my co-pending application Serial 274,976 which was filed May 22, 1939. More particularly it relates to materials for the storing and utilization of the heat evolved in an exothermic reaction for use in carrying out endothermic reactions. The invention relates especially to the use of low melting mixtures comprising metal halides.

The invention is particularly useful when employed in connection with reactions wherein the exothermic reaction and the endothermic reaction or change are of the same order of magnitude insofar as heat evolution and consumption are concerned, and wherein the temperatures at which these reactions take place are within the same approximate range.

Among the types of processes in which the present invention is usefully employed are catalytic cracking, catalytic dehydrogenation, cyclization of aliphatic hydrocarbons, etc. All of these reactions are endothermic in character and during the course of the conversions are accompanied by the deposition of non-volatile carbonaceous material on the catalytic masses used to assist the conversion. It is common practice to remove the carbonaceous deposits from the catalyst surfaces by heating the catalytic masses at temperatures in excess of 500 C. in the presence of oxygen-containing gases, whereby the carbon is oxidized to carbon monoxide and carbon dioxide. This reaction is accompanied by an evolution of heat which must be conducted from the system to prevent damage to both the equipment and the catalyst masses. In many cases, the heat evolved during this reactivation step is sufficient or nearly suflicient to supply that required for the processing step. Normally in carrying out catalytic proceses of this type, the processing and-reactivation steps are carried out alternately in the form of a cycle wherein the processing reaction is carried out for a definite period of time, and the reactivation step is carried out for another definite.

In many In one specific embodiment the present invention comprises heat exchange media comprising mixtures of cuprous chloride with anhydrous metallic halides, said mixtures melting substantially below the point at which the reaction in which it is used occurs and preferably below 450 C., said mixtures being particularly useful in catalytic processes wherein the heat from an exothermic reaction is removed and used in an endothermic reaction.

The mixtures used in the present invention and which may comprise eutectics as well as other mixtures should desirably have the following characteristics:

(1) A low melting point whereby they can be maintained in the liquid state at relatively low temperatures when not in actual use. If the melting point is too high, dimculties may arise either in pumping or in otherwise handling, due to freezing. The melting point must necessarily be well below the temperature at which they are used.

(2) The salt mixture should be thermally stable at any temperature which is likely to be reached during the course of the reaction. Normally this includes temperatures up to 600 C. or higher.

(3) They should be stable in contact. with air or minor amounts of moisture, and should not form high melting products in contact with these materials at ordinary or elevated temperatures for long periods of time.

(4) The mixtures should be non-corrosive to ordinary steel or ferro-alloy equipment. This is, of course, essential both from the standpoint of the equipment involved, and loss of chemicals which might occur due to failure of the equipment during the process.

(5) The constituents should not react with explosive violence with hydrocarbons in case of accidental contact therewith such as might be caused by failure. of the equipment, or due to contamination of the salt mixture with organic materials under any circumstances.

(6) The constituents of the mixture should be relatively inexpensive.

(7) The boiling point should be well above the temperatures likely to be reached during any step of the process in which it is employed. Likewise, the vapor pressure should be low so that high pressures need not be-applied to maintain the material in substantially liquid form.

(8) The material should have high specific heat, giving good heat storage capacity, and high degree of heat conductivity.

(9) It should be relatively non-poisonous and non-corrosive to the skin so that it does not introduce undue hazards during handling.

The following is a list of some salt mixtures comprised within the scope of the invention, together with their melting points:

The melting points of the combinations listed can be varied still further by the addition thereto of suitable amounts of a third component. The use of such ternary mixtures is included within the scope of the present invention. Although it is preferred to employ a lower melting mixture, any combination melting below the temperature at which it is to be used and fulfilling the other requirements of a heat exchange media as given above can be used in the present invention. The reactions in which these media are employed normally take lace at temperatures substantially above 450 C., but need not be limited to that temperature.

The mixtures may be further characterized to include (a) cuprous chloride plus anhydrous mono-valent metallic halides having melting points below 1000 C., (b) cuprous chloride plus anhydrous bi-vaient metallic halides melting below 500 0., and (c) cuprous chloride plus anhydrous tri-valent metallic halides melting below 300-400 C.

The relatively low melting points of these mixtures permit their being maintained in liquid form by moderate heating, and in many cases high pressure steam is suflicient so that the danger of freezing of lines, and solidification of the are operated in cycles of alternating periods, and wherein the molten salt surrounds the tubes or chambers wherein the catalyst is disposed, means being provided for the pumping of the molten salt from a region of high temperature to a region of lower temperature, and vice versa. In another type of equipment, the reactor may comprise a multiplicity of tubes containing catalytic masses, the tubes being arranged so that a part are in the process stage while the remainder are in the reactivation stage. The heat exchange medium surrounds the tubes and is circulated by mechanical means. Another type of reactor may employ chambers, normally operated in pairs, wherein the catalyst mass is disposed. The heat exchange medium is circulated through tubes passing through the catalyst bed, and the molten salt from one reactor to another. Additional heat may be supplied or removed from the heat exchange medium by passage of a portion of the molten salt through heaters or coolers as may be desired.

Although the mixtures described herein are particularly useful in connection with catalytic reactions, it is intended that they shall be used as thermophoric materials generally.

The following example is given to illustrate the usefulness and practicability of the invention, but should not be construed as limiting it to the exact conditions given therein.

The heat exchange medium comprised a mixture of approximately 10 parts by weight of cuprous chloride and 3.5 parts by weight of potassium chloride. The molten mixture was circulated through a salt bath in which vertical catalyst tubes were disposed. Connected to this reactor was a second similar reactor. One reactor was used for catalytically cracking a Mid-Continent gas oil at 500 0., while the second reactor whichhad previously been used for this purpose was being simultaneously reactivated by passing a mixture of air and flue gas containing approximately 3% oxygen through the tubes containing the cracking catalyst. The temperature of reactivation was maintained at a maximumof 750 C. while the temperature of processing was maintained at 500 C. At inter vals of one hour, the operations were switched so that the spent catalyst was reactivated while the freshly reactivated catalyst was used for processing, thus making a continuous cycle. The molten heat exchange medium was circulated between the two reactors in such a' manner that the heat evolved in the reactor undergoing reactivation was transferred to supply the heat necessary for carrying out the processing cycle in the companion reactor. In this manner it was possible to materially reduce the heat consumption of the catalytic cracking process, and also to extend the life of the catalytic mass by an appreciable amount, since at no time was the temperature of reactivation permitted to exceed the safe upper limits of approximately 700-800 C.

The catalytic mass used in carrying out this process was a precipitated, sodium-free, silicaalumina-zirconia catalyst.

I claim as my invention:

1. In processes forutilizing the heat evolved during an exothermic reaction for the carrying out ofan endothermic reaction by circulation of a heat exchange medium, the improvement which comprises using a mixture of cuprous chloride with an anhydrous halide of a polyvalent metal as the heat-carrying medium. 7

2. In processes for utilizing the heat of reaction in an exothermic reaction to supply the heat for an endothermic reaction, the improvement comprising using a binary mixture of cuprous chloride and an anhydrous halide of a polyvalent metal as the heat-carrying medium.

3. In processes for utilizing the heat of reaction in an exothermic catalytic reaction occurring at a temperature in excess of 500 C. to supply the heat for an endothermic catalytic reaction occurring at a temperature in excess of 450 C., the improvement comprising the use of a mixture of cuprous chloride with an anhydrous halide of a polyvalent metal, said mixture having a melting point below 450 C. as a heat exchange medium.

4. In processes for utilizing the heat of reaction from an exothermic reaction occurring at a temperature in excess of about 500 C. for carrying out a reaction occurring at a temperature in excess of about 450 C., the improvement which comprise the use of a mixture of cuprous chloride and anhydrous halide of a polyvalent metal, said mixture having a melting point below 450 C. as a heat exchange medium.

5. In a process for utilizing the heat evolved during the reactivation of a carbonized catalytic mass for carrying out an endothermic catalytic reaction, the improvement which comprises using a mixture of cuprous chloride and an anhydrous halide of a polyvalent metal as a heat carrying medium, said mixture melting below 450 C.

6. In a catalytic cracking process wherein the catalyst is alternately used to crack hydrocarbon oil followed by a period of reactivation by treatment with an oxygen-containing gas and the heat evolved during said reactivation being utilized to supply a part of the heat necessary for cracking said oil, the improvement which comprises using a mixture of cuprous chloride and an anhydrous halide of a polyvalent metal melting below approximately 450 C. asthe heat carrying medium.

7. The process of claim 1 further characterized by using a mixture of cuprous chloride and an anhydrous halide of a bivalent metal.

8. The process of claim 1 further characterized by using a mixture of cuprous chloride and an anhydrous halide of a trivalent metal.

9. In processes for utilizing the heat of reaction of an exothermic reaction for efiecting an endothermic change occurring at'a substantially lower temperature than said exothermic reaction,

, the improvement comprising the use of a mixture of cuprous chloride with an anhydrous halide of a polyvalent metal, said mixture melting below the temperature at which said endothermic change occurs.

CHARLES L. THOMAS. 

